CN101558175A - Cavitation process for products from precursor halides - Google Patents
Cavitation process for products from precursor halides Download PDFInfo
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- CN101558175A CN101558175A CNA200780030200XA CN200780030200A CN101558175A CN 101558175 A CN101558175 A CN 101558175A CN A200780030200X A CNA200780030200X A CN A200780030200XA CN 200780030200 A CN200780030200 A CN 200780030200A CN 101558175 A CN101558175 A CN 101558175A
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- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
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Abstract
A precursor halide compound is reduced to a predetermined product at substantially ambient conditions. The halide is added to an anhydrous liquid reaction medium containing one or more alkali metals or alkaline earth metals as reductants. The metal reductants are dispersed as very small globules in the liquid by cavitation of the liquid, such as by application of high intensity ultrasonic vibrations or high-shear mixing to the reaction vessel. Continued cavitation of the liquid medium affects low temperature reduction of the precursor halide(s) to produce a metal, metal alloy, metal compound, ceramic material, metal matrix-ceramic composite material, or the like. The practice may be applied, for example, to titanium tetrachloride, alone or with other chlorides, to produce titanium metal, titanium alloys (for example Ti-6A1-4V), and titanium compounds (TiSi2).
Description
Technical field
[0001] the present invention relates under basic envrionment temperature, adopt cavitation process in the anhydrous liq medium by hydride precursor preparation metal, metal alloy and compound, stupalith and metal matrix.Basic metal or the alkaline-earth metal that is fit to can be dispersed in the described liquid medium with the reduction precursor halide by cavitation.For example, can prepare titanium, titanium alloy and titanium compound, platinum alloy and transition metal silicide.In illustrative examples, practice relates to titanium chloride or with the mixture of titanium chloride and other precursor halide to be added in the liquid that contains the reductive agent material of cavitation, to prepare metal titanium or titanium alloy or titanium compound.
Background technology
[0002] titanium and metal alloy thereof are to prepare to get up relatively costly material at present.Titanium alloy can be used to prepare goods with the form such as foundry goods, forging and sheet material.Can prepare titanium base material good strength performance and combining than light weight are provided.For example, titanium alloy is used to make aircraft.Since with have the iron alloy that can compete performance is compared titanium with aluminium alloy cost problem, so the use of titanium alloy in Motor vehicles is restricted.
[0003] titaniferous ore is carried out ore dressing to obtain to be fit to the TiO of concentration
2In chloridization process, titanium dioxide (rutile crystal form often) by in fluidized-bed reactor in the presence of the coke (carbon) chlorination to make titanium tetrachloride (TiCl
4), it is volatile liquid at room temperature.Traditionally, metal titanium is with sodium or magnesium metallic high temperature reduction titanium tetrachloride (TiCl with batch process
4) make.Pure metal titanium (99.9%) is to be passed through in 1910 in steel cylinder in 700-800 ℃ of heating sodium and TiCl by Matthew A.Hunter at first
4And preparation.Be used for technical scale make first kind of metal titanium and still the technology of extensive employing be Kroll technology.In Kroll technology, 800 ℃-900 ℃ magnesium is used as TiCl
4The reductive agent of steam, and as by product generation magnesium chloride.These two kinds of technologies all generate titanium sponge and all need the molten again step of vacuum arc of the very power consumption repeatedly titanium of purifying.When the alloying component can when form was introduced, these technologies can be used to produce simultaneously titanium and one or more additional metals (alloy) with the suitable chloride salt (or other halide salts that is fit to) that bears the sodium that carries out with titanium tetrachloride vapors or magnesium reduction reaction.The technology output fine titanium metal and the metal alloy of these high temperature and power consumption, but as mentioned above, as the application in vehicle parts, these titanium materials are too expensive for many application examples.
[0004] Armstrong/ITP technology uses basic metal or alkaline-earth metal to come reducing metal halogenide equally in the manufacturing of metal.Armstrong technology can be moved in lower temperature, and can be used as the successive processes operation to make metal or metal alloy (as titanium or titanium alloy) powder.But the projected cost of metal is still very high, and is still too high for many road vehicle application.
[0005] technology is made titanium and titanium alloy and titanium compound more cheaply.If the technology cheaply that is applicable to other metal and alloy and compound can be provided, will be useful especially.
Summary of the invention
[0006] by near envrionment temperature with near in liquid reaction medium, using reductive agent metallic reducing halogenated titanium (for example, titanium tetrachloride) under the barometric point, can prepare metal titanium (as an example).Adopt suitable cavitation (cavitation) operation, for example sonochemical process or high shear mixing are assisted the reduction of precursor halide in reaction medium.Described technology also can be used for reducing simultaneously halogenated titanium and other precursor halide to make titanium alloy or titanium compound or titanium metal groundmass composite material.In addition, according to selected precursor halide or precursor halide combination, described technology can be used for making numerous other materials of many forms.
[0007] described reaction medium is a liquid anhydrous, suitable low-vapor pressure, and itself and described precursor halide or described reductive agent metal do not have reactivity.The example of the reaction medium material that is fit to has anhydrous liquid hydrocarbon such as naphthalane, 1,2,3,4-tetralin, decane, dodecane and n-Hexadecane.The example of the reaction medium material that is fit to also has liquid state to contain silicone oil, as polydimethyl silane, and ionic liquid at room temperature.Described liquid medium can be with the dry and anhydrous rare gas element of anaerobic such as helium or argon gas perfusion or cover so that inert atmosphere to be provided in treating processes basically.
[0008] the described reductive agent that is used for described precursor halide is suitably one or more basic metal or alkaline-earth metal such as lithium, sodium, potassium, rubidium, caesium, magnesium, calcium and barium.Preferred reductive agent be can near envrionment temperature by apply ultrasonic vibration is dispersed in the reactant in the described liquid medium as colloid low-melting mixtures to described liquid.For example, the eutectic mixture of sodium and potassium such as Na
0.22K
0.78And Na
0.44K
0.56In about room temperature is liquid, and is effective reductive agent of precursor halide.Then with one or more precursor halide,, add in the described reaction medium with dispersive reductive agent, and be reduced into predetermined product as titanium tetrachloride.When precursor halogenide comprises halogenated titanium, product can, for example, be mixture or the titaniferous alloy or the titanium compound of metal titanium, titanium and other metal.
[0009] this process using cavitation process (preferably sonochemistry operation) with the reductive agent dispersion of materials in liquid medium and promote the reduction of precursor halide.Use produces frequency usually greater than the energy converter of about 20 kilo hertzs sound wave in liquid, the fitted vessel that contains described liquid medium is imposed ultrasonic vibration.Acoustic energy causes that micro-bubble is concatenated to form, grows and breaks within described liquid, thereby forms the local center of excessive temperature and pressure, bulk liquid is produced the rate of cooling that is exceedingly fast.Preferably described liquid medium has lower vapour pressure in treatment temp, and this medium can provide steam in the high-temperature zone in cavitation bubble hardly thus.Simultaneously, the introducing of rare gas element in liquid promoted not form cavitation bubble (cavitation bubble) by at high temperature do not have reactive little atom in described bubble.
[0010] this cavitation process at first is dispersed in the reductive agent metal in the hydrocarbon liquid, promotes the reaction of reducing metal and precursor halide then when precursor halide and described liquid come in contact.Composition according to the halogenide parent material, the particle that the halogenide that is reduced produces metal, metal alloy, metallic compound or metal matrix or the like (when precursor halogenide is, or comprises certainly,, nonmetal during as tetracol phenixin or silicon tetrachloride, product can be nonmetal).Metal content in the reductant (reducing medium) is oxidized to corresponding alkali metal or alkaline earth metal halide salt.Reaction is carried out several minutes usually to a few hours, and the described processed halid metal component of basal ration productive rate is provided usually.
[0011] thus, for instance, titanium tetrachloride liquid is passed into and contains finely divided Na
0.22K
0.78N-Hexadecane in, product is titanium metal, sodium-chlor and Repone K.
[0012] separate solid from described reaction medium, and from described metallic product (or other predetermined product), separate described salt.How many temperature of liquid medium has raise some from the environment starting temperature, arrives about 100 ℃ temperature but only be elevated to about 60 ℃ usually.Described reaction can be carried out in batches or continuously.
[0013] for example using, the example of the product of this technology of titaniferous halide vapor comprises metal titanium, titanium and is used to form other metal of alloy such as mixture and the titanium compound such as the titanium silicide (TiSi of aluminium and/or vanadium
2).Also can make other metal such as platinum and zirconium and their alloy and compound.In described technology, also can use non-metallic halide precursor such as tetracol phenixin or silicon tetrachloride.Product is made as nano sized particles at first often.Product is amorphous often or very small crystal size.
[0014] technology can carried out near the temperature of envrionment temperature and with lower energy consumption as described in this practice was as the remarkable advantage of metal, metal alloy and metallic compound, intermetallic compound and metal matrix etc. for Production Example.
Description of drawings
[0015] Fig. 1 is that embodiment of the present invention are at the schema that is applied to begin to make as halide precursors with titanium tetrachloride titanium metal.
[0016] Fig. 2 is the device synoptic diagram that is used for using the sodium that is dispersed in liquid hydrocarbon and potassium mixture sonochemistry reduction titanium chloride.
Embodiment
[0017] the present invention utilizes sonochemistry to promote precursor halide to be reduced into useful products such as metal, metal alloy, compound, pottery, mixture and metal matrix.When carrying out the sonochemistry operation, liquid is subjected to high-intensity sound or ultrasonic (sound frequency is higher than 20 kilo hertzs, exceeds human earshot).Liquid is accommodated in the suitable container, and described container is by drivings such as one or more ultrasonic energy energy converters.Each energy converter will be higher than 20 kilo hertzs AC energy and convert the mechanical vibration of frequency much at one to.Described energy converter utilizes magnetostriction or piezoelectric to convert alternating-current to mechanical vibration usually.
[0018] when applying the ultrasonic vibration that is fit to intensity, energy is passed to liquid by wall of container.Ultrasonic energy causes cavitation bubble small within described liquid to be concatenated to form, to grow and break, and forms the local center of excessive temperature and pressure, bulk liquid is produced the rate of cooling that is exceedingly fast.According to estimates, local temperature and the pressure in the bubble can reach 5000K and two kilobars respectively.Ultrasonicly propagate by a series of compressions and sparse (rarefactions) that brings out in the liquid medium that passes at it.Under enough big power, the power that produces in sparse circulation exceeds the magnetism between the fluid molecule, forms cavitation bubble.Bubble will be grown up by the process that is known as rectified diffusion in acoustic cycles subsequently, and rectified diffusion (rectified diffusion) promptly enters bubble and in compression process and not exclusively be discharged from from a small amount of steam of medium and gas in the expansion stages of bubble.Bubble is grown up to reaching unsettled size always, breaks in ensuing compression process (being acoustic half-cycle) then, releases energy to realize chemistry and mechanic effect.The diameter of spherical bubbles or vapor cavity can be about 0.2 to about 200 microns, and instantaneous temperature can be about 5000K.Vapor cavity is surrounded by liquid shell, liquid shell and being immersed in the bulk liquid.The thickness of described liquid shell can be about 0.02 to about 2 microns, and instantaneous temperature can be about 2000K.Bulk liquid can be heated gradually by sonochemical activity.Suppose that bulk liquid is initially located in low temperature, 298K for example, it can reach the temperature of 670K at the most in sonochemical process process for a long time.
[0019] chemical reaction can occur in two kinds of different zones of medium: (1) in described vapor cavity, promptly described bubble itself, within, (2) are within the hot liquid shell environment of described bubble.The huge temperature difference between the narrow width of hot liquid shell and vapor cavity and the surrounding liquid (approximately 5000K) has caused extremely steep thermograde, and this then is converted into about 10
9The rate of cooling of K/s.That this condition will cause forming will be metastable-and be non-crystalline state-metal, alloy and compound sometimes.
[0020] with basic metal and magnesium the chemical reduction of metal chloride was for example being put into practice in the industrial production at titanium metal under the high temperature.But the invention enables can reduction be fit under the temperature that is lower than the temperature that is used to synthetic a certain concrete product traditionally precursor halide.In enforcement of the present invention, sonochemistry is used to promote the reduction of precursor halide in inert, anhydrous liquid reaction medium.Preferably, reaction medium is the anhydrous hydrocarbon of low-vapor pressure, as naphthalane, 1,2,3,4-tetralin, decane, dodecane and n-Hexadecane.Some fusing point is well below 0 ℃ in these liquid, and boiling point is considerably beyond 100 ℃.Thus, they provide the wide temperature range that is lower than and is higher than the typical environment temperature as reaction medium.Preferred low-vapor pressure is so that minimized from existing of the steam of liquid reaction medium in the cavitation bubble.For some embodiment, the hydrocarbon with moderate vapor pressure may also be fit to as dimethylbenzene and toluene.Water-content in the described anhydrous liquid reaction medium is preferably lower than 10ppm compatibly less than 100ppm.
[0021] precursor chloride is formed the element (or element combinations) of expectation by the reduction of basic metal or alkaline-earth metal and the reaction of basic metal or alkaline earth metal chloride is heat release.The heat that a certain amount of precursor discharged in given reaction can be determined by thermochemical calculation.For batch treatment, the heat that the amount of reacting required liquid reaction medium (being solvent sometimes) is discharged by reaction and as the specific heat decision of the liquid of reaction medium.Typically, select amount of liquid so that when reaction finishes temperature raise not exceed and be regarded as safe or desirable preset temperature restriction.This program is applicable to continuous processing, and prerequisite is that reaction unit is furnished with heat exchanger.In this case, must select precursor to add speed, make the heat release rate during reduction reaction and the heat extraction velocity balance of heat exchanger.
[0022] generally speaking, may be preferably be in envrionment temperature or begin to handle during near envrionment temperature at reaction medium.It is found that basic metal or alkaline-earth metal reductive agent cause the temperature of medium to raise by means of the dispersion of ultrasonic wave (or other cavitation process) in reaction medium, and be higher 10 ℃-30 ℃ than its starting temperature usually.The interpolation of precursor halide causes the temperature in the reaction vessel constantly to raise under cavitation conditions, thereby the temperature of reaction medium typically reaches temperature between 70 ℃-100 ℃ when reaction finishes.Several specific embodiments of the present invention's practice are as described below.In the embodiment of these less relatively reaction volumes, when the temperature of reaction medium does not attempt to control its temperature when room temperature raises.But when target was to make product to obtain predetermined particle size and/or form, the medial temperature of control reaction medium may be desirable or essential.Typically, low average reaction medium temperatures produces less titanium products particle, and its feature is higher specific surface area and higher chemical reactivity usually.When forming in the reaction medium at lesser temps, described particle may be non-crystalline state or have a minimum crystalline structure.On the other hand, higher average response medium temperature helps forming and has lower specific surface area and lower chemically reactive larger particles.These higher thermotonus conditions produce crystalline product sometimes and are in agglomerating particles (aggregated particle) form.The temperature that is fit to can be selected from, for example about-80 ℃ to about 300 ℃.
[0023] except the temperature of reaction medium, the power input of unit surface is the factor of another one decision product particle size and form.The power input of unit surface also is the parameter of decision cost.If the expected result of reaction is given particle size and form, then must the conditioned reaction temperature and power input realize this target (after having selected suitable solvent or reaction medium).Yet if the low cost of requirement, people will wish to operate under the critical power near reaction so.This critical power can come to determine by experiment, promptly by operation successive reaction under the power level that successively decreases up to reaction stop or overall treatment time long.Ultrasonic energy is input as low or medium level.
[0024] in the laboratory scale titanium tetrachloride reductive example that this specification sheets is hereinafter described, in reaction flask or container and surface energy converter engagement, the energy converter energy level is 0.25 watt/cm
2Described surface.
[0025] phonochemical reaction is to use rare gas element, compatibly helium or argon gas, continous pouring or spray into that reaction medium carries out.Rare gas element promotes cavitation and provides protective layer for liquid reaction medium.With regard to the degree in the high temperature field that enters cavitation bubble with regard to the atom or the molecule of rare gas element, these chemical species remain unchanged probably and do not pollute the reaction product of expectation.The aperture typical case of injection component is in the scope of about 0.5 μ m-200 μ m.
[0026] basic metal and alkaline-earth metal (particularly magnesium) can be used as reductive agent.But, two kinds of eutectic alloys of sodium and potassium, Na
0.22K
0.78And Na
0.44K
0.56In any one all be preferred because each all is liquid under typical envrionment conditions and utilizes ultrasonic energy to be dispersed in the anhydrous liquid hydrocarbon medium as colloid (or thinner) easily.Preferably use the reducing metal of the form in the liquid reaction medium that is dispersed in easily.In addition, also preferably before adding halide precursors, the reductive agent metal is dispersed in the reaction medium usually.
[0027] is the precursor halide of gas or volatile reactive fluid or solid form by the reduction of sonochemistry ground.The example of precursor gases is boron trichloride (BCl
3).The example of liquid precursor halides has titanium tetrachloride (TiCl
4), vanadium tetrachloride (VCl
4), tetracol phenixin and silicon chlorides (SiCl
4And Si
2Cl
6).The solid precursor halogenide that not exclusively is insoluble to described liquid phonochemical reaction medium is fit to too.Example comprises platinum dichloride (PtCl
2), dibrominated platinum (PtBr
2), platinum diiodide (PtI
2), aluminum chloride (AlCl
3), titanous chloride (TiCl
3), Tetrachloroplatinum (PtCl
4) and zirconium tetrachloride (ZrCl
4).
[0028] makes non-crystalline state or nanocrystalline product, for example comprised Ti, TiSi
2, Zr, PtZr and PtTi.
[0029] will use the volatile liquid titanium tetrachloride as representational precursor halide, n-Hexadecane low-melting mixtures (eutectic mixture, Na as representational inertia low-vapor pressure hydrocarbon liquid and sodium and potassium
0.22K
0.78) as reductive agent, for example understand embodiment of the present invention.With reference to the accompanying drawings described technology is described.Fig. 1 is the schema that is used to form with separation of titanium metal product, and Fig. 2 is the reactor assembly synoptic diagram that is used for described technology.
[0030] schema of Fig. 1 has generally illustrated the processing step of making predetermined product by the reduction precursor halide.In this embodiment, for making titanium metal, precursor halide is a titanium tetrachloride.Described technology can be carried out in batches or continuously.
[0031], is used for filling cavitation reactor from the appropriate amount of fluid reaction medium of solvent storage tank with reference to Fig. 1.Set up cavitation conditions in the liquid medium of energy in cavitation reservoir of use from suitable ultrasonic energy energy converter etc.Use is at the pump and the flow control of inert gas flow, and rare gas element such as argon gas or helium are sprayed the liquid reaction medium that passes in the cavitation reactor.As shown in the figure, preferably rare gas element is circulated in the cavitation reactor so that volatile constituent is stayed in the reactor so that the loop line is round.
[0032], be the liquid mixture (NaK) of sodium and potassium metal at this, from the NaK input source adds liquid reaction medium in the cavitation reactor to an amount of reductive agent.The content that can make cavitation reactor is through over-heat-exchanger, to remove energy (at Fig. 1 work " power " of getting the bid) and controlled temperature.
[0033] in separator, product stream is carried out separating treatment.In separating step, the solid of titaniferous, sodium-chlor and Repone K is removed from reaction medium, and described reaction medium is used as solvent recycled in solvent tank.Clean described solid (Ti, NaCl and KCl) to remove halide salts (as the solution of NaCl+KCl).From described cleaning step, reclaim titanium metal and deliver in the moisture eliminator of power consumption to obtain exsiccant pure titanium metal (Ti output).In the vaporizer of power consumption, handle the solution or the suspension of sodium-chlor and Repone K, to reclaim and these salt of recirculation (NaCl+KCl output) possibly.
[0034] through too small suitable modification, above-mentioned technology also is applicable to many products that can obtain by the combination of many independent precursor halide compound or precursor halide compound.
[0035] above-mentioned technology is carried out in laboratory-scale apparatus as shown in Figure 2.
[0036] reaction vessel 12 is partially immersed in the vibration bath 34 of ultrasonic generator 10.Ultrasonic generator vibration bath 34 contains the anhydrous mixture of naphthalane and n-Hexadecane.
[0037] reaction vessel 12 contains liquid reaction medium 32, and described in this embodiment liquid reaction medium 32 is a n-Hexadecane.Certain amount of fluid Na
0.22K
0.78Eutectic alloy is used as colloidal droplets and is dispersed in the described hexadecane reaction medium 32.Reaction vessel 12 (transparent Glass Containers) is by 14 sealings of gastight feed through system lid.Comprise thermometer 16 in the container.Hexadecane reaction medium 32 is used gas supply line 22B, mister head 24, gas backstreaming pipeline 22A, needle-valve 26 and barrier film air pump 26 and passes the argon gas that feed through system capping 14 is annotated with extremely dried and anaerobic.Use the pressure of needle-valve 28 and pressure warning unit 30 control argon gas atmosphere.
[0038] ultrasonic generator 10 started about 20 minutes, and described sodium-potassium mixture is dispersed in the initial limpid hexadecane reaction medium 32 as colloidal droplets.The drop of reductive agent metal, cavitation bubble and argon gas bubbles are all very little, do not show in Fig. 2.Soliquid becomes opaque indigo plant-grey.Ultrasonic generator 10 continuation effects are slowly added liquid titanium tetrachloride 36 to the reaction medium 32 by the interpolation pipe 18 that inserts resistance to air loss feed through system lid 14 from syringe 20.Definite titanium tetrachloride amount of being added, so that according to chemically suitable with the amount of following formula and sodium/potassium reductive agent, TiCl
4+ 4Na
0.22K
0.78→ Ti+0.88NaCl+3.12KCl.
[0039] in this embodiment, 1.252 gram (35.20mmol) Na
0.22K
0.78Be dispersed in the 125ml n-Hexadecane.0.566g (8.80mmol) TiCl then
4Be added in the described dispersive reductive agent metal.
[0040] along with the carrying out that reacts, the blackening of reaction vessel content.In about halfhour time, add titanium chloride.Because the input and the described thermopositive reaction of acoustic energy, the temperature of the material in the uncolled container (except that the thermosteresis in ambient air) is elevated to about 80 ℃ from about 25 ℃.Total time of insonating is 60 minutes.Close ultrasonic generator 10 and make the content sedimentation of reaction vessel 12.
[0041] after about one hour product particles settling, removes clear solvent above the black powder by decant.Clean solid to remove remaining n-Hexadecane with toluene, mixture is carried out centrifugation.Remove washing lotion by decant, carry out the second time with pentane and clean and sepn process, dry in vacuum drying oven then.Determine that by the X-ray diffraction described salt is sodium-chlor and Repone K, and determine they in described reduction reaction with quantitative formation.Other product of described reductive of titanium tetrachloride is essentially the amorphous state titanium-cuprum metal.
[0042] cleans the solid of described reactionless medium so that sodium-chlor is separated with titanium products with Repone K with methane amide subsequently.Use at the anhydrous solvent of metal chloride in case with any titanium chloride reaction that does not consume.In other embodiments of the present invention, can make water remove alkali halide salts or alkaline earth salt.
[0043] by centrifugation the product powder is separated from the formamide soln of described sodium and sylvite.The described amorphous state titanium-cuprum metal of heating in vacuum drying oven is to remove remaining solvent and washing fluid.Can in vacuum drying oven or other heating unit that is fit to, further heat described metal then so that described metallic product is heat-treated.For example, can be to metallic product annealing, crystallization, fusion or casting or the like.
[0044] can make amendment to above-mentioned reaction unit, to realize temperature control to this reaction vessel and/or round-robin argon gas or other inert gas atmosphere.In addition, also can be come and gone when being circulated in described reaction vessel it is washed, to remove oxygen and liquid hydrocarbon reaction medium material at described circulated inert gas.In gas backstreaming pipeline 22A, between mister head 24 and barrier film air pump 28, can insert the oxygen washer.
[0045] embodiment of lifting has been made titanium metal by the precursor halide charge that only contains titanium tetrachloride.Certainly, titanium has numerous useful application in many industries.Also can form described titanium products by other titanium halide.Halogenated titanium reductive product can anneal, handle with powder metallurgy process processing, heat or cold working or other, to convert it into the predetermined required metallurgy form of using.
[0046] also can comprise halogenated titanium and implement described technology by use than the precursor halide mixture of one or more other precursor halide of small part, to form reduzate, described reduzate is the reduzate of the mixture of titanium and for example aluminium and vanadium, as the preparation of the titanium-aluminum-vanadium alloys that forms titanium.Equally, by using mixture of halides such as titanium tetrachloride and silicon tetrachloride, can form titanium compound such as titanium silicide (TiSi
2).
[0047] by this cavitation process, in inert anhydrous response liquid medium, use precursor halide and basic metal and/or alkaline-earth metal reductive agent, can form other metallic product.For example, made following material by above-mentioned laboratory scale technology.
[0048] according to reaction ZrCl
4+ 4Na
0.22K
0.78→ Zr+0.88NaCl+3.12KCl has made zirconium powder.Liquid reaction medium is the n-Hexadecane of 150mL envrionment temperature.Dispersive sodium/potassium mixture amount is 0.057g (29.72mmol).The zirconium tetrachloride amount of adding in described dispersive reductive agent metal is 1.735g (7.43mmol).Insonate the time (after NaK disperses) be 20 hours.In described technology, obtained the zirconium metal-powder of basal ration output by zirconium tetrachloride.
[0049] according to reaction TiCl
4+ 2SiCl
4+ 12Na
0.22K
0.78→ TiSi
2+ 2.64NaCl+9.36KCl makes the titanium disilicide powder.Liquid reaction medium is the n-Hexadecane of 150mL envrionment temperature.Dispersive sodium/potassium mixture amount is 1.274g (35.81mmol).Add 0.566g (0.325mL, 2.98mmol) TiCl
4Together with 1.014g (0.660mL, 5.97mmol) SiCl
4The total amount of precursor is 2.85g, and the total amount of product is 2.81g.Insonate the time (after NaK disperses) be 60 minutes.
[0050] according to formula PtCl
4+ ZrCl
4+ 8Na
0.22K
0.78→ PtZr+1.76NaCl+6.24KCl has made platinum zirconium powder end.Liquid reaction medium is the n-Hexadecane of 125mL envrionment temperature.Dispersive sodium potassium mixture amount is 1.21g (34.00mmol).Add 1.43g (4.25mmol) Tetrachloroplatinum and 0.99g (4.25mmol) zirconium tetrachloride.Total insonate the time (after NaK disperses) is 16 hours.Obtained the platinum-zirconium mixed powder of basal ration output by its halide precursors.
[0051] thus, though recorded and narrated some specific embodiments, can obviously find out disclosedly to be used for metal halide reductive sonochemistry operation and to have widely and use.
Claims (20)
1. reduce at least a precursor halide compound with the method for production predetermined product, this method comprises:
The exsiccant rare gas element is cycled through anhydrous liquid reaction medium and bring out cavitation in described liquid reducing medium; With
In described liquid reaction medium, at least a precursor halide compound is being mixed with reducing agent composition during the cavitation, so that described precursor halide compound is reduced into described predetermined product, described reducing agent composition is reacting the halide salts that the described reducing agent composition in back is converted to described basic metal and/or alkaline-earth metal substantially by at least a composition the in basic metal and/or the alkaline-earth metal with described precursor halide compound.
2. the method for at least a precursor halide compound of reduction according to claim 1, wherein in described cavitation and described precursor halide in the reduction process of described predetermined product, described liquid reaction medium is maintained at-80 ℃ of temperature to about 300 ℃ of scopes approximately.
3. the method for at least a precursor halide compound of reduction according to claim 1, wherein said liquid reaction medium is in envrionment temperature at first.
4. the method for at least a precursor halide compound of reduction according to claim 1, wherein said anhydrous liq be hydrocarbon liquid, comprise the liquid or the ionic liquid of silicon-containing compound.
5. the method for at least a precursor halide compound of reduction according to claim 1, wherein said anhydrous liq are the hydrocarbon liquid that is selected from naphthalane, 1,2,3,4-tetralin, decane, dodecane and n-Hexadecane.
6. the method for at least a precursor halide compound of reduction according to claim 1, wherein said reducing agent composition is made up of the mixture of sodium and potassium substantially.
7. the method for at least a precursor halide compound of reduction according to claim 1, wherein said reducing agent composition are substantially by being that the liquid sodium and the mixture of potassium are formed being lower than about 30 ℃ temperature.
8. the method for at least a precursor halide compound of reduction according to claim 1, wherein said reductive agent compound is dispersed in the described liquid reaction medium at first, and described precursor halide compound is added in the described liquid reaction medium subsequently.
9. the method for at least a precursor halide compound of reduction according to claim 1, the amount of wherein said liquid reaction medium pre-determines according to the reaction heat of described precursor halide and described reductive agent material.
10. the method for at least a precursor halide compound of reduction according to claim 1, the precursor halide and the reducing agent composition that wherein are stoichiometric ratio basically react.
11. the method for at least a precursor halide compound of reduction according to claim 1, wherein rare gas element is given by described liquid reaction medium by pump in loop.
12. reduce at least a precursor halide compound with the method for production predetermined product, this method comprises:
By utilizing vibration to realize that in anhydrous liq cavitation will be dispersed at the reducing agent composition of described precursor halide not in the described anhydrous liq with described reducing agent composition reaction, formation is at the reduction reaction medium of described precursor halide, and described reducing agent composition is substantially by at least a composition the in basic metal and/or the alkaline-earth metal;
The exsiccant rare gas element is cycled through described reduction reaction medium to be given an account of the cavitation in the matter and volatile materials is returned described reduction reaction medium with auxiliary block post; And continue described vibration simultaneously,
In described reaction medium, add described at least a precursor halide, described precursor halide be reduced into described predetermined product and form the corresponding halide salts of described basic metal and/or alkaline-earth metal simultaneously.
13. the method for at least a precursor halide compound of reduction according to claim 12, wherein said precursor halide compound are muriate.
14. the method for at least a precursor halide compound of reduction according to claim 12, wherein said anhydrous liq be hydrocarbon liquid, comprise the liquid or the ionic liquid of silicon-containing compound.
15. the method for at least a precursor halide compound of reduction according to claim 12, wherein said anhydrous liq are the hydrocarbon liquid that is selected from naphthalane, 1,2,3,4-tetralin, decane, dodecane and n-Hexadecane.
16. the method for at least a precursor halide compound of reduction according to claim 12, wherein said reducing agent composition is made up of the mixture of sodium and potassium substantially.
17. the method for at least a precursor halide compound of reduction according to claim 12, wherein said reducing agent composition are substantially by being that the liquid sodium and the mixture of potassium are formed being lower than about 30 ℃ temperature.
18. the method for at least a precursor halide compound of reduction according to claim 12, wherein in described cavitation and described precursor halide in the reduction process of described predetermined product, described liquid reaction medium is maintained at approximately-80 ℃ to about 300 ℃ temperature.
19. the method for at least a precursor halide compound of reduction according to claim 12, the precursor halide and the reducing agent composition that wherein are stoichiometric ratio basically react.
20. the method for at least a precursor halide compound of reduction according to claim 12, wherein said precursor halide are chloride cpd and described predetermined product is a kind of in ti powder, titanium disilicide powder, platinum zirconium powder end or the zirconium powder end.
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| US11/465,180 US7465333B1 (en) | 2006-08-17 | 2006-08-17 | Cavitation process for products from precursor halides |
| US11/465,180 | 2006-08-17 |
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| CN101558175A true CN101558175A (en) | 2009-10-14 |
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| US (1) | US7465333B1 (en) |
| CN (1) | CN101558175A (en) |
| DE (1) | DE112007001934B4 (en) |
| WO (1) | WO2008021684A2 (en) |
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| CN104561607A (en) * | 2015-01-13 | 2015-04-29 | 朝阳金达钛业股份有限公司 | Method for producing carbon-containing titanium sponge and device thereof |
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| US8753418B2 (en) * | 2009-06-12 | 2014-06-17 | The United States Of America, As Represented By The Secretary Of The Navy | Sonochemically mediated preparation of nanopowders of reactive metals |
| WO2011139436A1 (en) | 2010-05-07 | 2011-11-10 | B9 Plasma, Inc. | Controlled bubble collapse milling |
| US8101152B1 (en) | 2010-08-18 | 2012-01-24 | GM Global Technology Operations LLC | Sonochemical synthesis of titanium-containing oxides |
| CN103687685A (en) * | 2011-05-16 | 2014-03-26 | 波士顿电子材料有限公司 | Manufacturing and applications of metal powders and alloys |
| CZ2012646A3 (en) * | 2012-09-19 | 2014-02-19 | Vysoké Učení Technické V Brně | Process for preparing magnetically conducting powders by making use of cavitation and apparatus for making the same |
| US10294552B2 (en) | 2016-01-27 | 2019-05-21 | GM Global Technology Operations LLC | Rapidly solidified high-temperature aluminum iron silicon alloys |
| US10260131B2 (en) | 2016-08-09 | 2019-04-16 | GM Global Technology Operations LLC | Forming high-strength, lightweight alloys |
| US10519531B2 (en) | 2017-02-17 | 2019-12-31 | Gm Global Technology Operations Llc. | Lightweight dual-phase alloys |
| US11035026B2 (en) | 2017-09-26 | 2021-06-15 | GM Global Technology Operations LLC | Aluminum iron silicon alloys having optimized properties |
| CN108031861A (en) * | 2017-12-18 | 2018-05-15 | 中国科学院深圳先进技术研究院 | Metal nano material and preparation method thereof |
| CN114686710A (en) | 2020-12-30 | 2022-07-01 | 通用汽车环球科技运作有限责任公司 | Grain refiner for magnesium-based alloys |
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| CN104561607A (en) * | 2015-01-13 | 2015-04-29 | 朝阳金达钛业股份有限公司 | Method for producing carbon-containing titanium sponge and device thereof |
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| US20080295645A1 (en) | 2008-12-04 |
| WO2008021684A2 (en) | 2008-02-21 |
| DE112007001934B4 (en) | 2011-01-27 |
| US7465333B1 (en) | 2008-12-16 |
| DE112007001934T5 (en) | 2009-06-25 |
| WO2008021684A3 (en) | 2008-11-27 |
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